The photooxidation of allyl chloride

The photooxidation of allyl chloride was studied by irradiation either in 100‐L Teflon bags or in a 22.7‐m3 Teflon smog chamber in the presence of added NOx. In the absence of added hydrocarbons, the reaction involves a Cl atom chain, which leads to a highly reactive system. A reaction mechanism is presented to account for the following photooxidation products: chloroacetaldehyde, formaldehyde, 1,3‐dichloroacetone, 3‐chloroacrolein, acrolein, glyoxal, chloroperoxyacetyl nitrate, and peroxypropenyl nitrate. The rate constant for OH reaction with allyl chloride at 298 K was measured by a relative rate method under conditions where the Cl atom chain length was small and was found to be kOH = 1.7 × 10−11 cm3 molecule−1 s−1. The rate constant for O3 reaction with allylchloride at 298 K was found to be kO3 = 1.5 × 10−18 cm3 molecule−1 s−1.